WO2015110492A1 - Process for the generation of thin inorganic films - Google Patents

Process for the generation of thin inorganic films Download PDF

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Publication number
WO2015110492A1
WO2015110492A1 PCT/EP2015/051181 EP2015051181W WO2015110492A1 WO 2015110492 A1 WO2015110492 A1 WO 2015110492A1 EP 2015051181 W EP2015051181 W EP 2015051181W WO 2015110492 A1 WO2015110492 A1 WO 2015110492A1
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Prior art keywords
compound
general formula
tert
butyl
ligand
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PCT/EP2015/051181
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English (en)
French (fr)
Inventor
Ke Xu
Christian Schildknecht
Jan SPIELMANN
Jürgen FRANK
Florian BLASBERG
Martin GÄRTNER
Daniel LÖFFLER
Sabine Weiguny
Kerstin Schierle-Arndt
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Basf Se
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Application filed by Basf Se filed Critical Basf Se
Priority to KR1020167023277A priority Critical patent/KR20160113667A/ko
Priority to CN201580006067.9A priority patent/CN107075678A/zh
Priority to JP2016548706A priority patent/JP2017505858A/ja
Priority to SG11201606042SA priority patent/SG11201606042SA/en
Priority to US15/114,666 priority patent/US20160348243A1/en
Priority to RU2016134923A priority patent/RU2016134923A/ru
Priority to EP15701181.8A priority patent/EP3099837A1/en
Publication of WO2015110492A1 publication Critical patent/WO2015110492A1/en
Priority to IL246810A priority patent/IL246810A0/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/04—Nickel compounds
    • C07F15/045—Nickel compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/06—Cobalt compounds
    • C07F15/065—Cobalt compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
    • C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages

Definitions

  • the present invention is in the field of processes for the generation of thin inorganic films on substrates, in particular atomic layer deposition processes.
  • Thin inorganic films serve different purposes such as barrier layers, seeds, liners, dielectrica, or separation of fine structures.
  • Several methods for the generation of thin inorganic films are known. One of them is the deposition of film forming compounds from the gaseous state on a substrate. In order to bring metal or semimetal atoms into the gaseous state at moderate temperatures, it is necessary to provide volatile precursors, e.g. by complexation the metals or sem- imetals with suitable ligands. These ligands need to be removed after deposition of the com- plexed metals or semimetals onto the substrate.
  • WO 2012 / 057 884 A1 discloses nitrogen-containing ligands for transition metals and their use in atomic layer deposition methods.
  • JP 2001 261 638 A discloses metal complex compounds which have a diimino pyrrolyl ligand useful as catalyst for an alpha olefin polymerization.
  • An object of the present invention was to provide a process for the generation of thin inorganic films on solid substrates by depositing metals or semimetals from the gaseous or aerosol state. It was desired that this process can be performed with as little decomposition of the precursor comprising the metal or semimetal as possible while the precursor is brought into the gaseous or aerosol state. At the same time it was desired to provide a process in which the precursor is easily decomposed after deposited on a solid substrate. A further object was to provide a pro- cess which is applicable for a broad variety of different metals or semimetals. It was also aimed at providing a process to generate high quality films under economically feasible conditions.
  • R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are independent of each other hydrogen, an alkyl group, or a trialkylsi- lyl group,
  • n is an integer from 1 to 3
  • M is a metal or semimetal
  • X is a ligand which coordinates M
  • n is an integer from 0 to 4.
  • the present invention also relates to a compound of general formula (I), wherein R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are independent of each other hydrogen, an alkyl group, or a trialkylsi- lyl group,
  • n is an integer from 1 to 3
  • M is Sr, Ba, Co, or Ni
  • X is a ligand which coordinates M
  • n is an integer from 0 to 4.
  • the present invention also relates to the use of a compound of general formula (I), wherein
  • R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are independent of each other hydrogen, an alkyl, or a trialkylsilyl group,
  • n is an integer from 1 to 3
  • M is a metal or semimetal
  • X is a ligand which coordinates M
  • n is an integer from 0 to 4 for a film formation process on a solid substrate.
  • R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are independent of each other hydrogen, an alkyl group, or a tri- alklylsilyl group. It is believed that the number of carbon atoms of ligand L influences the ease with which the compound of general formula (I) can be brought into the gaseous or aerosol state without significant decomposition.
  • the absence of significant decomposition in the context of the present invention means that at least 90 wt.-% of the compound of general formula (I) can be brought into the gaseous or aerosol state without chemical change, more preferably at least 95 wt.-%, in particular at least 98 wt.-%.
  • all alkyl and/or trialkylsilyl groups of the ligand L together contain up to twelve carbon atoms, more preferably up to eight.
  • An alkyl group can be linear or branched. Examples for a linear alkyl group are methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n- nonyl, n-decyl.
  • Examples for a branched alkyl group are iso-propyl, iso-butyl, sec-butyl, tert- butyl, 2-methyl-pentyl, 2-ethyl-hexyl, cyclopropyl, cyclohexyl, indanyl, norbornyl.
  • a trialkylsilyl group can bear the same or different alkyl groups. Examples for a trialkylsilyl group with the same alkyl groups are trimethylsilyl, triethylsilyl, tri-n-propylsilyl, tri-iso-propylsilyl, tricyclohexylsi- lyl.
  • R 1 and R 6 are according to the present invention independent of each other an alkyl or a trialkylsilyl group without a hydrogen atom connected to the carbon or silicone bond to the imino-nitrogen atom of ligand L.
  • the ligand L is believed to be more stable against rearrangement or cleavage at elevated temperatures, such as at more than 100 °C, in particular at more than 150 °C.
  • thermo gravimetry under an inert atmosphere as described in DIN 51006 (Thermische Analyse (TA) - Thermogravimetrie (TG) - Kunststoffn, July 2006), wherein the more precise procedure A for the temperature control is preferred. If the compound of general formula (I) loses less than 10 %, preferably less than 5 % of its weight when heated to its vaporization temperature, it is considered to be thermally stable at this temperature. It is particularly preferred that R 1 and R 6 are independent of each other tert-butyl or trimethylsilyl groups.
  • R 3 and R 4 are according to the present invention independent of each other hydro- gen or a short alkyl group or a trimethylsilyl group.
  • Examples for a short alkyl group are methyl, ethyl, n-propyl and iso-propyl.
  • the complex is likely to become less bulky. It is more preferred that both R 3 and R 4 are hydrogen. The complex presumably packs even more effi- ciently if R 2 and R 5 are independent of each other hydrogen, a short alkyl group, or a trimethylsi- lyl group.
  • R 2 and R 5 are independent of each other hydrogen, a short alkyl group, or a trimethylsilyl group, such as in particular hydrogen, methyl, ethyl, n- propyl, iso-propyl, or trimethylsilyl. It is more preferred that R 2 and R 5 are independent of each other hydrogen or methyl, it is more preferred that R 2 and R 5 are both hydrogen. It is also more preferred that R 2 and R 5 are both methyl. In this case, it is believed that the ligand L shows higher stability against fragmentation when heated to high temperatures such as more than 100 °C, in particular to more than 150 °C. It is preferred that the molecular weight of the compound of general formula (I) is up to 1000 g/mol, more preferred up to 900 g/mol, even more preferred up to 800 g/mol, in particular up to 700 g/mol.
  • the compound of general formula (I) according to the present invention can contain from 1 to 3 ligands L, i.e. n is an integer from 1 to 3. Generally, the bigger the metal or semimetal M is the higher n can get. Usually, n is up to 3 only for large M. This is the case if M is a metal or semi- metal from the fourth period or from higher periods of the periodic table of the elements. Preferably, n is from 1 to 2, more preferably n equals 2. M in the compound of general formula (I) can be according to the present invention any metal or semimetal.
  • Metals are Li, Be, Na, Mg, Al, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Rb, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, In Sn, Cs, Ba, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os Ir, Pt, Au, Hg, TI, Bi.
  • Preferred metals are Ni, Co, Ta, Ru, Cu, Sr, and Ba. More preferred metals are Sr, Ba, Co, or Ni.
  • Semimetals are B, Si, As, Ge, Sb.
  • the metal or semimetal M can be in any oxidation state.
  • M is close to the oxidation state in which it is supposed to be in the final film on the solid substrate.
  • the metal or semimetal M in the compound of general formula (I) should preferably be in the oxidation state 0 or -1 or +1 as long as a stable compound of general formula (I) is available. Otherwise the next higher or lower oxidation state is chosen with which a stable compound of general formula (I) can be obtains, such as -2 or +2.
  • the metal or semimetal M in the compound of general formula (I) is in the oxida- tion state +1 , +2, or +3.
  • M in the compound of general formula (I) should preferable be in the oxidation state +4 or +3 or +5. More preferably, M in the compound of general formula (I) has the same oxidation state as it is supposed to be in the final film on the solid substrate. In this case no oxidation or reduction is necessary.
  • the ligand X in the compound of general formula (I) can be according to the present invention any ligand which coordinates M. If X bears a charge, m is normally chosen such that the com- pound of general formula (I) is neutrally charged. If more than one such ligand is present in the compound of general formula (I), i.e. m > 1 , they can be the same or different from each other. If m > 2, it is possible that two ligands X are the same and the remaining X are different from these. X can be in any ligand sphere of the metal or semimetal M, e.g. in the inner ligand sphere, in the outer ligand sphere, or only loosely associated to M.
  • X is in the inner ligand sphere of M. It is believed that if all ligands X are in the inner ligand sphere of M the volatility of the compound of general formula (I) is high such that it can be brought into the gaseous or aerosol state without decomposition.
  • the ligand X in the compound of general formula (I) according to the present invention includes anions of halogens like fluoride, chloride, bromide or iodide and pseudohalogens like cyanide, isocyanide, cyanate, isocyanate, thiocyanate, isothiocyanate, or azide.
  • X can be any amine ligand in which the coordinating nitrogen atom is either aliphatic like in dialkylamine, piperidine, morpholine, or hexamethyldisilazane; amino imides;aromatic like in pyrrole, indole, pyridine, or pyrazine.
  • the nitrogen atom of the amine ligand is often deprotonated before coordinated to M.
  • X can be an amide ligand such as formamide or acetamide; an amidinate ligand such as acetamidine; or a guanidinate ligand such guanidine. It is also possible that X is a ligand in which an oxygen atom coordinates to the metal or semimetal.
  • alkanolates examples are alkanolates, tetrahydrofurane, acetylacetonate, acetyl acetone, 1 ,1 ,1 ,5,5,5- hexafluoroacetylacetonate, or 1 ,2-dimethoxyethane.
  • Other suitable examples for X include both a nitrogen and an oxygen atom which both coordinate to M including dimethylamino-iso- propanol.
  • ligands which coordinate via a phosphorous atom to M.
  • trialkyl phosphines such as trimethyl phosphine, tri-tert-butyl phosphine, tricyclohexyl phosphine, or aromatic phosphines such as triphenyl phosphine, or tritolylphosphine.
  • Suitable ligands X are alkylanions like methyl, ethyl, propyl or butyl anions.
  • X can also be an unsaturated hydrocarbon which coordinates with the ⁇ -bond to M.
  • Unsaturated hydrocarbons include ethylene, propylene, iso-butylene, cyclohexene, cyclooctadiene, ethyne, propyne. Terminal alkynes can relatively easily be deprotonated. Then they can coordinate via the termi- nal carbon atom bearing the negative charge.
  • X can also be an unsaturated anionic hydrocarbon which can coordinate both via the anion and the unsaturated bond such as allyl or 2- methyl-allyl.
  • Cyclopentadienyl anions and substituted cyclopentadienyl anions are also suitable for X.
  • Further suitable examples for X are carbonmonoxide (CO) or nitric oxide (NO). It is also possible to use molecules which contain multiple atoms which coordinate to M. Examples are bipyridine, o-terpyridine, ethylenediamine, substituted ethylenediamine, ethylene- di(bisphenylphosphine), ethylene-di(bis-tert-butylphosphine).
  • Small ligands which have a low vaporization temperature are preferred for X. These preferred ligands include carbonmonoxide, cyanide, ethylene, tetrahydrofurane, dimethylamine, trime- thylphosphine, nitric oxide and 1 ,2-dimethoxyethane. Small anionic ligands which can easily be transformed into volatile neutral compounds upon protonation, for example by surface-bound protons, are preferred for X. Examples include methyl, ethyl, propyl, dimethylamide, diethylamide, allyl, 2-methyl-allyl.
  • the compound of general formula (I) comprises two ligands L.
  • n equals 2.
  • m there is no ligand X present in the compound of general formula (I), i.e. m equals 0.
  • the compound of general formula (I) becomes general formula (la):
  • the two ligands L can either bear the same or different substituents for each R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 .
  • the same definitions for R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 apply as described above.
  • each R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 is the same substituent in both ligands L.
  • the compound of general formula (la) is chiral unless the substituents R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are such that at least one of the ligands L has C2v symmetry. This is, for example, the case if R 1 equals R 6 , R 2 equals R 5 , and R 3 equals R 4 which is generally preferred substitution pattern for the compound of general formula (I). If the compound of general formula (la) shows chirality, the compound can be used as racemic mixture or enan- tiomerically pure. The enantiomerically pure compounds of general formula (la) are preferred.
  • TMS stands for trimethylsilyl
  • TBDMS stands for tert-butyl-dimethylsilyl
  • THF stands for tetrahy- drofurane
  • bipy stands for 2,2'-bipyridine
  • PPh3 stands for triphenylphosphine
  • ⁇ 2 stands for dimethylamine
  • n-BuO stands for n-butoxy.
  • the compound of general formula (I) used in the process according to the present invention is used at high purity to achieve the best results.
  • High purity means that the substance used contains at least 90 wt.-% compound of general formula (I), preferably at least 95 wt.-% compound of general formula (I), more preferably at least 98 wt.-% compound of general formula (I), in particular at least 99 wt.-% compound of general formula (I).
  • the purity can be determined by elemental analysis according to DIN 51721 (Prufung fester Brennstoffe - Beêt des Geh-retes an Kohlenstoff und Wasserstoff -maschine nach Radmacher-Hoverath, August 2001 ).
  • the ligand L in which R 2 , R 3 , R 4 , R 5 are hydrogen can be synthesized by condensation of 2,5- dicarbonylpyrrole with the respective amines under typical imine formation conditions.
  • the precursor 2,5-dicarbonylpyrrole can be synthesized according to procedures of the following refer- ences:
  • the compound of general formula (I) is brought into the gaseous or aerosol state. This can be achieved by heating the compound of general formula (I) to elevated temperatures. In any case a temperature below the decomposition temperature of the compound of general formula (I) has to be chosen. Preferably, the heating temperature ranges from slightly above room temperature to 300 °C, more preferably from 30 °C to 250 °C, even more preferably from 40 °C to 200 °C, in particular from 50 °C to 150 °C.
  • Another way of bringing the compound of general formula (I) into the gaseous or aerosol state is direct liquid injection (DLI) as described for example in US 2009 / 0 226 612 A1 .
  • the compound of general formula (I) is typically dissolved in a solvent and sprayed in a carrier gas or vacuum.
  • a carrier gas or vacuum Depending on the vapor pressure of the compound of general formula (I), the temperature and the pressure the compound of general formula (I) is either brought into the gaseous state or into the aerosol state.
  • solvents can be used provided that the compound of general formula (I) shows sufficient solubility in that solvent such as at least 1 g/l, preferably at least 10 g/l, more preferably at least 100 g/l.
  • the aerosol comprising the compound of general formula (I) should contain very fine liquid droplets or solid particles.
  • the liquid droplets or solid particles have a weight average diameter of not more than 500 nm, more preferably not more than 100 nm.
  • the weight average diameter of liquid droplets or solid particles can be determined by dynamic light scattering as described in ISO 22412:2008.
  • Pressures can range from 100 to 10 "10 mbar, preferably from 1 to 10 "8 mbar, more preferably from 0.01 to 10 "6 mbar, in particular from 10 "3 to 10 "5 mbar such as 10 -4 mbar.
  • the pressure is 10 bar to 10 -7 mbar, more preferably 1 bar to 10 -3 mbar, in particular 0.01 to 1 mbar, such as 0.1 mbar.
  • a compound of general formula (I) is deposited on a solid substrate from the gaseous or aerosol state.
  • the solid substrate can be any solid material. These include for example metals, semimetals, oxides, nitrides, and polymers. It is also possible that the substrate is a mixture of different materials. Examples for metals are alu- minum, steel, zinc, and copper. Examples for semimetals are silicon, germanium, and gallium arsenide. Examples for oxides are silicon dioxide, titanium dioxide, and zinc oxide. Examples for nitrides are silicon nitride, aluminum nitride, titanium nitride, and gallium nitride. Examples for polymers are polyethylene terephthalate (PET), polyethylene naphthalene-dicarboxylic acid (PEN), and polyamides.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalene-dicarboxylic acid
  • the solid substrate can have any shape. These include sheet plates, films, fibers, particles of various sizes, and substrates with trenches or other indentations.
  • the solid substrate can be of any size. If the solid substrate has a particle shape, the size of particles can range from below 100 nm to several centimeters, preferably from 1 ⁇ to 1 mm. In order to avoid particles or fi- bers to stick to each other while the compound of general formula (I) is deposited onto them, it is preferably to keep them in motion. This can, for example, be achieved by stirring, by rotating drums, or by fluidized bed techniques.
  • the deposition takes place if the substrate comes in contact with the compound of general for- mula (I).
  • the deposition process can be conducted in two different ways: either the substrate is heated above or below the decomposition temperature of the compound of general formula (I). If the substrate is heated above the decomposition temperature of the compound of general formula (I), the compound of general formula (I) continuously decomposes on the surface of the solid substrate as long as more compound of general formula (I) in the gaseous or aerosol state reaches the surface of the solid substrate. This process is typically called chemical vapor deposition (CVD).
  • CVD chemical vapor deposition
  • an inorganic layer of homogeneous composition e.g.
  • the metal or the metal or semimetal oxide or nitride is formed on the solid substrate as the organic ma- terial is desorbed from the metal or semimetal M.
  • the solid substrate is heated to a temperature in the range of 300 to 1000 °C, preferably in the range of 350 to 600 °C.
  • the substrate is below the decomposition temperature of the compound of general formula (I).
  • the solid substrate is at a temperature lower than the temperature of the place where the compound of general formula (I) is brought into the gaseous or aerosol state, often at room temperature or only slightly above.
  • the temperature of the substrate is at least 30 °C lower than the place where the compound of general formula (I) is brought into the gaseous or aerosol state, more preferably at least 50 °C lower, in particular at least 100 °C lower.
  • the solid substrate is at a temperature higher than the temperature of the place where the compound of general formula (I) is brought into the gaseous or aerosol state.
  • the temperature of the substrate is at least 30 °C lower than the decomposition temperature of the compound of general formula (I).
  • the temperature of the substrate is from room temperature to 400 °C, more preferably from 100 to 300 °C.
  • the deposition of compound of general formula (I) onto the solid substrate is either a physisorp- tion or a chemisorption process.
  • the compound of general formula (I) is chemisorbed on the solid substrate.
  • the chemisorption is typically accompanied by the loss of at least one of the ligands X or L.
  • the loss of one of these ligands can be observed via infrared spectroscopy of the gas phase surrounding the solid substrate.
  • the mass increase is recorded by the eigen frequency of the quartz crystal.
  • the mass should not decrease to the initial mass, but about a monolayer of the residual compound of general formula (I) remains if chemisorption has taken place.
  • the x-ray photoe- lectron spectroscopy (XPS) signal (ISO 13424 EN - Surface chemical analysis - X-ray photoe- lectron spectroscopy - Reporting of results of thin-film analysis; October 2013) of M changes due to the bond formation to the substrate.
  • the deposition of the compound of general formula (I) on the solid substrate preferably represents a self- limiting process step.
  • the typical layer thickness of a self-limiting deposition processes step is from 0.01 to 1 nm, preferably from 0.02 to 0.5 nm, more preferably from 0.03 to 0.4 nm, in particular from 0.05 to 0.2 nm.
  • the layer thickness is typically measured by ellipsometry as descri- bed in PAS 1022 DE (Referenz compiler Kunststoff Betician von
  • the deposited compound of general formula (I) it is possible to expose the deposited compound of general formula (I) to oxygen, ozone, a plasma like oxygen plasma, ammonia, oxidants like nitrous oxide or hydrogenperox- ide, reductants like hydrogen, ammonia, alcohols, hydroazine, dialkylhydrazine or hydroxyla- mine; or solvents like water. It is preferable to use oxidants, plasma or water to obtain a layer of a metal oxide or a semimetal oxide. Exposure to water, an oxygen plasma or ozone is preferred. Exposure to water is particularly preferred. If layers of elemental metal or semimetal are desired it is preferable to use reductants.
  • ammonia or hydrazine Small molecules are believed to easily access the metal or semimetal M due to the planarity of the aromatic part of ligand L which is the consequence of the conjugation of the two iminomethyl groups to the pyrrole unit in ligand L. Typically, a low decomposition time and high purity of the generated film is observed.
  • a deposition process comprising a self-limiting process step and a subsequent self-limiting reaction is often referred to as atomic layer deposition (ALD).
  • ALD atomic layer deposition
  • Equivalent expressions are molecular layer deposition (MLD) or atomic layer epitaxy (ALE).
  • MLD molecular layer deposition
  • ALE atomic layer epitaxy
  • the process according to the present invention is preferably an ALD process.
  • a particular advantage of the process according to the present invention is that the compound of general formula (I) is very versatile, so the process parameters can be varied in a broad range. Therefore, the process according to the present invention includes both a CVD process as well as an ALD process.
  • the sequence of depositing the compound of general formula (I) onto a solid substrate and decomposing the deposited compound of general formula (I) is performed at least twice. This sequence can be repeated many times, for example 50 or 100 times. In this way films of a defined and uniform thickness are accessible. Typical films generated by repeating the above sequence have a thickness of 0.5 to 50 nm.
  • each sequence with the same compound of general formula (I) or with different compounds of general formula (I) or with one or more compounds of general formula (I) and one or more metal or semimetal precursors different from general formula (I).
  • M is Ba
  • every second, fourth, sixth and so on sequence is carried out with a Ti precursor, i.e. either a compound of general formula (I) or a different Ti comprising compound, it is possible to generate films of BaTi03.
  • films of various thicknesses are generated.
  • the thickness of the film is proportional to the number of sequences performed. However, in practice some deviations from proportionality are observed for the first 30 to 50 sequences. It is assumed that irregularities of the surface structure of the solid substrate cause this non-proportionality.
  • One sequence of the process according to the present invention can take from milliseconds to several minutes, preferably from 0.1 second to 1 minute, in particular from 1 to 10 seconds. The longer the solid substrate at a temperature below the decomposition temperature of the compound of general formula (I) is exposed to the compound of general formula (I) the more regular films formed with less defects.
  • the process according to the present invention is particularly suitable for the deposition of Ba, Sr, Co, or Ni on a solid substrate. Therefore, the present invention also relates to a compound of general formula (I), wherein R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are independent of each other hydrogen, an alkyl group, or a trialkylsi- lyl group,
  • n is an integer from 1 to 3
  • M is Sr, Ba, Co, or Ni
  • X is a ligand which coordinates M
  • n is an integer from 0 to 4.
  • the compound of general formula (I) is generally stable enough such that it can be easily purified for example by sublimation and be obtained in high purity.
  • High purity means that the substance used contains at least 90 wt.-% of compound of general formula (I), preferably at least 95 wt.-% of compound of general formula (I), more preferably at least 98 wt.-% of compound of general formula (I), in particular at least 99 wt.-% of compound of general formula (I).
  • the purity can be determined by elemental analysis as described above.
  • the present invention also relates to the use of a compound of general formula (I), wherein
  • R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are independent of each other hydrogen, an alkyl, or a trialkylsilyl group,
  • n is an integer from 1 to 3
  • M is a metal or semimetal
  • X is a ligand which coordinates M
  • m is an integer from 0 to 4 for a film formation process on a solid substrate.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , n, X, and m as described above apply.
  • a film is generated.
  • a film can be only one monolayer of deposited compound of formula (I), several consecutively deposited and decomposed layers of the compound of general formula (I), or several different layers wherein at least one layer in the film was generated by using the compound of general formula (I).
  • a film can contain defects like holes. These defects, however, generally constitute less than half of the surface area covered by the film.
  • the film is preferably an inorganic film. In order to generate an inorganic film, all organic ligands L and X have to be removed from the film as described above. More preferably, the film is an inorganic film of a metal oxide, a semimetal oxide, a metal nitride, or a semimetal nitride.
  • the film can have a thickness of 0.1 nm to 1 ⁇ or above depending on the film formation process as described above.
  • the film has a thickness of 0.5 to 50 nm.
  • the film preferably has a very uniform film thickness which means that the film thickness at different places on the substrate varies very little, usually less than 10 %, preferably less than 5 %.
  • the film is preferably a conformal film on the surface of the substrate. Suitable methods to determine the film thickness and uniformity are XPS or ellipsometry.
  • the film generated by the present invention can be used for an electronic element comprising the film.
  • the electronic element can have structural features of various sizes, for example from 100 nm to 100 ⁇ .
  • the process for forming the films for the electronic elements is particularly well suited for very fine structures. Therefore, electronic elements with sizes below 1 ⁇ are preferred.
  • Examples for electronic elements are field-effect transistors (FET), solar cells, light emitting diodes, sensors, or capacitors.
  • FET field-effect transistors
  • solar cells solar cells
  • light emitting diodes light emitting diodes
  • sensors or capacitors.
  • the film serves to increase the reflective index of the layer which reflects light.
  • An example for a sensor is an oxygen sensor, in which a film can serve as oxygen conductor, for example if a metal oxide film is prepared.
  • the film can act as dielectric layer or as diffusion barrier. It is also possible to make semiconductor layers out of films in which elemental nickel-silicon is deposited on a solid substrate. Furthermore, a cobalt-containing film, e.g. elemental cobalt, can be deposited by the process according to the present invention, for example as a diffusion barrier for copper-based contacts, such as Cu-W alloys.
  • Preferred electronic elements are capacitors.
  • the film made by the process according to the present invention has several possible functions in capacitors. It can for example act as dielectric or as interlayer between dielectric layer and conductive layer to enhance lamination. Preferably the film acts as dielectric in a capacitor.
  • the film has several possible functions in complex integrated circuits. It can for example act as interconnect or as interlayer between a conducting copper layer and an insulating metal oxide layer to decrease copper migration into the insulating layer. Preferably the film acts as interconnect in a field-effect transistor or as interlayer in electrical contacts in complex integrated circuits. Description of the Figures:
  • Figure 1 Thermogravimetric analysis of compound C1 , on the x-axis the temperature of the sample is given in °C, on the y-axis the remaining mass as percentage of the initial mass of the sample is given.
  • Figure 2 Thermogravimetric analysis of compound C2, on the x-axis the temperature of the sample is given in °C, on the y-axis the remaining mass as percentage of the initial mass of the sample is given.
  • the ligand L (2 molar equivalents) was dissolved in hexane. NaH (2 molar equivalents), suspended in hexane, was added to ligand L. The reaction mixture was stirred at room temperature for 24 h. For the Sr-containing compounds Sr (1 molar equivalent), for the Br-containing compounds Bab (1 molar equivalent), dissolved in THF, was then added to the mixture comprising ligand L. This mixture was stirred for 48 h. After Nal separation, the solvent was removed under reduced pressure. The pure compound of general formula (I) was isolated by vacuum sublimation (150 - 200 °C, 0.1 mbar).
  • the mass spectrum obtained by an electron impact spectrometer (solid sample, 70 eV beam, MSD detector) has its most intense peak at 370 amu and a peak of 20 % intensity at 602 amu.
  • thermogravimetric analysis was performed with about 20 mg sample. It was heated by a rate of 5 °C/min in an argon stream. The result of the thermogravimetric analysis is depicted in Figure 2.
  • the mass spectrum obtained by an electron impact spectrometer (solid sample, 70 eV beam, MSD detector) has its most intense peak at 552 amu and a peak of 70 % intensity at 320 amu.
  • the ligand L (0.891 g, 3.82 mmol, 2 molar equivalents) was dissolved in 40 mL dry THF and added to a suspension of KH (0.230 g, 5.73 mmol, 3 molar equivalents) in 40 mL dry THF. The reaction mixture was stirred at room temperature for 18 h. In a separate flask, NiBr2(dme) (0.608 g, 1 .91 mmol, 1 molar equivalent) was suspended in 50 mL THF. The suspension containing the potassium salt of ligand L was filtered and the clear filtrate was added to the suspension comprising the metal salt. This mixture was stirred for 24 hrs at room temperature giving a dark brown solution with a colorless precipitate.
  • thermogravimetric analysis was performed with about 20 mg sample. It was heated by a rate of 5 °C/min in an argon stream. The result of the thermogravimetric analysis is depicted in Figure 3.
  • the suspension containing the potassium salt of ligand L was filtered and the clear filtrate was added to the suspension comprising the metal salt. This mixture was stirred for 24 hrs at room temperature giving a dark red-brown solution with a colorless precipitate. After separation of the colorless potassium salt, the solvent was removed under reduced pressure. The solid brown residue was extracted with 100 ml. toluene and solids were separated by filtration. The filtrate was again evaporated under reduced pressure giving 0.628 g of a solid crude product. The dark red colored pure compound (0.458 mg, 46% yield) was isolated by vacuum sublimation (160 - 170 °C, 0.5 mbar).
  • the ligand L (1 .0 g, 3.83 mmol, 2 molar equivalents) was dissolved in 20 mL dry THF and add- ed to a suspension of KH (0.16 g, 4.02 mmol, 2.1 molar equivalents) in 30 mL dry THF. The reaction mixture was stirred at room temperature for 18 h. In a separate flask, Sr (0.65 g, 1 .91 mmol, 1 molar equivalent) was dissolved in 30 mL THF. The solution containing the potassium salt of ligand L was added to the solution comprising the strontium salt. This mixture was stirred for 24 hrs at room temperature giving a white suspension. After separation of the color- less potassium salt, the solvent was removed under reduced pressure. The pure compound (250 mg, 22 % yield) was isolated by vacuum sublimation (160-180 °C, 10 "3 mbar).
  • the ligand L (1 .0 g, 3.83 mmol, 2 molar equivalents) was dissolved in 20 mL dry THF and added to a suspension of KH (0.16 g, 4.02 mmol, 2.1 molar equivalents) in 30 mL dry THF. The reaction mixture was stirred at room temperature for 16 h. In a separate flask, Bab (0.75 g,

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RU2016134923A RU2016134923A (ru) 2014-01-27 2015-01-22 Способ образования тонких неорганических пленок
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US10850982B2 (en) 2015-04-29 2020-12-01 Basf Se Stabilization of sodium dithionite by means of various additives

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MX2017009473A (es) 2015-01-20 2017-11-02 Basf Coatings Gmbh Proceso para la produccion de laminados flexibles organicos-inorganicos.
EP3408273B1 (en) 2016-01-27 2020-06-17 Basf Se Process for the generation of thin inorganic films
EP3957769A1 (en) * 2017-12-20 2022-02-23 Basf Se Process for the generation of metal-containing films
US11377454B2 (en) * 2018-04-17 2022-07-05 Basf Se Aluminum precursor and process for the generation of metal-containing films

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Cited By (3)

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US10850982B2 (en) 2015-04-29 2020-12-01 Basf Se Stabilization of sodium dithionite by means of various additives
KR20190029595A (ko) * 2016-07-18 2019-03-20 바스프 에스이 합토-3-펜타다이엔일 코발트 또는 니켈 전구체 및 이의 박막 증착 공정에서의 용도
KR102445367B1 (ko) * 2016-07-18 2022-09-20 바스프 에스이 합토-3-펜타다이엔일 코발트 또는 니켈 전구체 및 이의 박막 증착 공정에서의 용도

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